Two distinguishable lithium sites in the zeolite Li-ZSM-5 as revealed by adsorption of CO: an infrared spectroscopic and thermodynamic characterisation
文献情報
B. Bonelli, E. Garrone, B. Fubini, B. Onida, M. Rodríguez Delgado, C. Otero Areán
By combining FTIR spectroscopic and microcalorimetric measurements on adsorbed CO, two lithium sites were found to be present in the zeolite Li-ZSM-5. Both of these sites, LiA and LiB, form Li(CO)+ monocarbonyl species with adsorbed CO; the corresponding C–O stretching frequencies are 2193 and 2187 cm−1, respectively. Formation of LiA(CO)+ involves an estimated adsorption enthalpy of ΔH° ≅ − 44 kJ mol−1, while for LiB(CO)+ the corresponding value is evaluated to be ΔH° ≅ −18 kJ mol−1. The large difference between these ΔH° values is explained in terms of an endothermic process occurring during formation of the LiB(CO)+ species, which involves a slight movement of the corresponding Li+ ion (away from its equilibrium position among oxygen anions of the zeolite framework). Formation of dicarbonyls is also discussed, as well as formation of O-bonded Li(OC)+ species.
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